Process for producing gasoline and the like



J. C. CLANCY.

PROCESS FOR PRODUCING GASOLINE AND THE LIKE. APPLICATION HLED JULY 3|. 1919.

1,4233%, Patented July 25, 1922.

as 4 g J na-comm cmnemor NIAGAM rams, NEW YORK, Ass

GEN CORPOTION, OF PROVIDENCE, RHODE ISLAND, A CORPORATION OF RHODE ISLAND,

Application filed .l'uly 31,

To all whom it may concern:

cracking hydrocarbons, and has for one of its objects the provision of a method capable of converting kerosene, or the like,'into more highly volatile substances, such as gasoline.

Another object of the invention is to so cure a higher percentage of conversion of the heavier hydrocarbons into lighter hydrocarbons having lower boiling points, than, to the best of my knowledge, has hitherto been po'ssible,at least in one'operation.

I further aim to utilize a volatile catalyst in said conversion, in such fashion as to dill avoid substantial Waste or loss of such catalyst.

These and other objects of my invention, such as improved product,will be hereinafter referred'to and the novel comb-inations of steps which constitute the improved process will be more especially pointed out in the appended claims.

In the drawing which forms part hereof, I have diagrammatically-exemplified a preferred apparatus in which my procem may be eflbctuatedybut as I am aware of various changes and modifications which may be made in said process and apparatus, without departing'from-the spirit of my invention, I desire to be limited only by the scope of said claims, broadly considered in the light of my disclosure. f 'f w I Insaiddrawi ng: I The figure a p-0W5, diagrammatically, an exceedingly simple apparatus inlwhich, preferably, kerosenemay be, convrt'e iin'to gasoline. In said apparatus the vapor "of hydro up via pipe Efrem-fa 'suitahle-soiirceof such vapor, suohas a still 2." Pipe' l ispreferably made to I serve. as a mixing chamber steam, air, or ran-equivalent oxygen supplying medium, being introduced into said chamber Specification of Letters Patent.

rnoc'nss roa rnonucmeeasonmn AND HE LIKE.

Patented- July 25,- 1922.

1919. Serial 210. 314,434.

through apipe 3, Assteam, acting conointly with the vaporous catalyst, tends to afford a higher yield of high grade gasoline, I prefer steam to air. It also tends to reduce the formation of the olefines and deposition of carbon; although when using my novel catalyst, I find little of this latter, especially when an adequate supply of oxygen is afi'orded; the oxygen combining with the excess carbon to form carbon monoxid. I

I do not wish to be limited to the employmerit of an oxygen supplying medium in my process; since the vaporous catalyst is capable of performing its function even when oxygen is not present. I greatly prefer, however, to supply an adequate amount of oxy gen, for reasons above noted; 4

The mixture of,-l.et us say, kerosene vapor and steam is quite complete by the time that it emerges from pipe 1 into the reaction chamber 4. This latter may conveniently be I formed of a pipe of considerably larger diameter than that designated 1.

To the lower end of pipe 4 is fastened a receptacle 5; the jointure between said receptacle and pipe being gas-tight and the receptacle being, further, preferably covered with heat insulation 6,e. g. magnesia, asbestos, or the like.

'lVithin' the receptacle 5 is a heating element 7, of any suitable description, although I preferto use an electrically heated element h vapor of mercury passes p and =mixes intimately with the mixture of hydrocarbon to be, treated, e; g. ke ro'seri e,passedj,carbon vapor and steam, aforesaid, and the OR TO THE NITRO- condensed and uselessly returned to the proc lighter hydrocarbons are to be formed, the temperature'is correspondingly raised.

The'reaction proceeds vigorously'in the superheating zone and gradually abates as the gaseous mixture flows thence up through the cooling section 4 of pipe 4. By the time that the gases reach the upper end of pipe 4, much of the mercury vapor has condensed; but as it settles down by gravity into the superheating zone, it again volatilizes and reascends with the incoming hydrocarbon vapor, to thus continue to circulate in pipe 4c as long as the process is conducted in the manner described.

.The hydrocarbon Vapor, now rich in gasoline, passes over, together with some mercury vapor, through pipe 11 into the con denser 12, in thecoil 12 of which, the remaining mercury-vapor is liquefied.

Of course, some mercury will be condensed in pipe 11 and most of this will flow back into pipe 4; while the liquid mercury formed in coil 12 will flow down into the trap and thence back by way of pipe 14 to the receptacle 5. y

The gasoline and other light hydrocarbons are cooled sufficiently to free them from mercury, and, if desired, from most of the residual heavy hydrocarbons which, for any reason have not been sufliciently reacted upon by the catalytic mercury vapor. Such heavy hydrocarbons will flow, along with the mercury, via the return pipe 14 to recep-' tacle 5, in which they Will normally promptly be volatilized for return to the process.

The condenser may be sufiiciently cooled by air or other suitable cooling fluid; the cooling medium passing into the casing 12 through pipe 15' and out through pipe 16. ,Care should be exercised to avoid undue cooling of pipe 12, however, since in such case obviously a part of the lighter hydrocarbons might be ess via pipe 14. The temperature to be maintained in the gas passing off, from the trap through pipe 17, will depend upon the product desired and also, of course, upon the pressure at which the operatlon is conducted. a

Pressure favors the efficient reaction of the vaporous catalyst upon the heavier hydrocarbons. Then, too, in a relatively small and inexpensive apparatus, with a condenser of but moderate size, the cracking operation may be conducted at a higher temperature,

- since the increase in pressure substantially correspondingly raises the boiling point of the mercury. and, of course, the temperature at which it condenses.

.In addition, high pressure favors the-return of insufliciently cracked hydrocarbons to the process via pipe 14. I

When the operation is not conducted under sub atm0spheric pressure (and Iprefer to increase rather than decrease the pres-1 sure, although even sub-atmospheric pressures may be employed) the temperature to be maintained in the receptacle 5 will in any casehave to be above the boiling pointof mercury to wit, 357.33 (1., and it is desirable-to not greatly exceed 600 C., in the superheating zone 4', although as high as from 650 to about (700 C., may be reached, especially if the operation be conducted under relatively high pressure.

The provision of the superheating zone 4:, favors the condensation of the mercury returned through pipe 14, in that the temperature maintained in said receptacle is not so greatly in excess of the boiling point of the mercury at the given pressure.

The superheating zone 4 may be constistituted by surrounding pipe 4 at this point by a mufile 18, preferably of heat resistant material; a torch 19, or its equivalent, being employed as thesource of heat. When a torch is used, the gases of combustion escape from the muflle by way of pipe 20.

The eneral course of the preferred mode of con uctin the process may now be'briefly reviewed: aporous kerosene is supplied from, for example, a fire still; steam or air being admixed with this vapor, preferably, although not necessarily, after the kerosene vapor has left the still. Mercury vapor, ascending from the receptacle 5, is then mixed with the previous mixture and .the whole vaporous mass is subjected in the superheating zone 4, to' a temperature preferably approximating 600 C., the vaboth to crack the heavier oils and to enable the hydrogen afforded by the steam (or supplied in any other manner desired'),and that resulting from the cracking of said heavier oils,.to hydrogenate the unsaturated hydrocarbons present to light naphtha and gasoline.

Itis noteworthy duced by this simple operation is clear and substantially free from the offensive odor which usually characterizes cracked gasoline and which requires additional treatment with sodium, or the like.

A further noteworthy feature is that. whereas when aluminium chlorid is used as a catalyst for cracking oils, in a known manner, it loses its. efiicacy within a comparatively short time and becomes converted into a blackcoke-like mass,in the present process the deposition or formation of carbon deposit, or coke, is so small, when the operation is conducted in the preferred manner herein described, as to be substantially negligible; and, in'any case, even when carthat the gasoline probon deposits form,as may occur, especially much as 60% or more of the kerosene supplied to the process being converted into clear, high grade gasoline, the olefine content of which is normally low, as a result of the potency of my novel catalyst in favoring the hydrogenation of the light unsaturated hydrocarbons by the tree hydrogen present under the described conditions.

I accordingly do not wish to be limited merely to the cracking of hydrocarbons, since in certainphases of my process hydrogenation is involved and in general the product to be formed will depend upon the temperature and pressure employed, and, of course, to a considerable measure, the molecular constitution of the hydrocarbon or hydrocarbons initially supplied to the process.

Having thus described my invention,what I claim is:

1. The process of cracking hydrocarbons, which comprises subjecting a hydrocarbon oil, while in vaporous condition, to the catalytic action of mercury vapor.

2. The process of cracking hydrocarbons, which comprises subjecting a hydrocarbon oil, while in vaporous condition, to the action of mercury vapor, condensing said mercury vapor and separating the mercury from the hydrocarbon product formed.

3. The process of cracking hydrocarbons, which comprises subjecting the hydrocarbon to be treated, to the action of heat while in the presence of mercury vapor and steam.

4c. The process of cracking hydrocarbons, which comprises subjecting vaporous kerosene to the catalytic action of vaporous mercury, at a temperature approximating alow red heat.

5. The process of cracking hydrocarbons, which comprises subjecting vaporous kerosene to the action of vaporous mercury, condensing said mercury and returning it to the process. 6. The process of changing the molecular constitution of a hydrocarbon, which com- I prises subjecting said hydrocarbon to heat in the presence of mercury, vapor acting as a catalyst.

7. The process of changing the molecular constitution of a hydrocarbon, which comprises subjecting said hydrocarbon to a temperature above 357 C. and below 700 C'., in the presence of mercury.

8. The process of changing the-molecular constitution of a hydrocarbon, which comprises subjecting said. hydrocarbon, while under super-atmospheric pressure, to a temperature above 857 C. and below 700 C., in the presence of mercury.

9. The process of cracking hydrocarbons which comprises subjecting said hydrocarbons while under pressure to the catalytic action of mercury vapor.

10. The process of cracking hydrocarbons which comprises heating said hydrocarbons under pressure in the presence of mercury vapor and steam.

11-. The process of cracking hydrocarbons which comprises vaporizing said hydrocarbons and causing the hydrocarbon vapors to mingle with mercury vapor while traversing a passage the temperature of which is higher than the boiling point of mercury.

12. The process of cracking hydrocarbons which comprises subjecting said hydrocarbons to the catalytic action of mercury vapor at a temperature above the normal boilingwhich comprises subjecting said hydrocarbons to the catalytic action of mercury vapor under pressure and at a temperature above the normal boiling point of mercury.

14. The process of changing the molecular constitution of a hydrocarbon which comprises subjectiiig said hydrocarbon to heat in the presence of: hydrogen and mercury vapor.

15. The process of changing the molecular constitution of a hydrocarbon which comprises subjecting said hydrocarbon, while under super-atmospheric pressure, to the action of hydrogen and mercury vapor.

In testimony whereof I have aflixed my signature, in the presence of two witnesses.

JOHN COLLINS CLANC'Y.

Witnesses:

EnsoN PORTER PFOBF, C. J. GoRR. 

